Cosmetic



' Patented Mar. 12, 1940 UNITED STATES PATENT OFFICE No Drawing.Application November 30, 1938, Serial No. 243,099

19 Claims.

This invention relates to cosmetic preparations and is particularlyconcerned with improvements in such preparations as cosmetic creams,including cold creams, vanishing creams, tissue creams,

anti-perspiration creams, lip-sticks, so-called lip rouges, pomades,shaving creams of the brushless and lathering type; hair washes and hairshampoos; dentifrices such as tooth pastes, tooth powders, liquiddentifrices, mouth washes, and

0 the like.

Conventional preparations of the type of cold creams, vanishing creams,shaving creams, and the like, contain a fatty constituent, generally inthe form of oils, fats, higher fatty acids such as stearic acid, waxes,and similar materials of a generally oleaginous material. Vanishingcreams, shaving creams, and similar preparations also contain relativelylarge proportions of water whereas lip sticks, lip rouges and the likeare devoid of an aqueous constituent. Soap or other alkaline materialwhich may or may not be converted into a soap in the finished product islikewise a very common constituent of creams of the type described.

The usual tooth pastes and tooth powders frequently contain soap orother saponaceous materials such as saponines, Turkey-red oil, and thelike, and materials such as precipitated chalk, dicalcium phosphate,tricalcium phosphate, kieselguhr, borax, perborates, peroxides, boricacid,

magnesium carbonate, and other known ingredients.

It is well recognized that soaps and the like possess variousobjectionable properties such as disagreeable taste, instability,relatively poor foaming or lathering properties in the limitedproportions which can be used, and, in the case of tooth pastes, atendency to cause a hardening thereof. Hair washes or shampoos are alsoof various types but a common example of an ordinary shampoo comprisesan aqueous solution of a liquid soap, such as a soap of cocoanut oilfatty acids.

Such preparations are unsatisfactory, among other things, in that theirlathering properties are severely diminished when they are used in thepresence of hard water and, in addition. scums of insoluble salts offatty acids comprising the original soap form in the hair and areexceedingly difiicult to remove. Another class of hair shampooscomprises an aqueous solution of Turkey-red oil or similar sulphonatedoils. These products have several objections among which is theirfailure to foam or lather and, in addition, they are sensitive tohardness in water. Recentfore known.

1y, so-called soapless shampoos have been oil'- ered on the market inthe form of aqueous solutions of certain so-called wetting agents. Whileovercoming many of the objections to the shampoos previously known andemployed, they still I leave something to be desired. In.particular,most of the so-called soapless shampoos have the objection of causing adrying out of the hair or scalp.

In accordance with the present invention, cosmetic preparations of thetype described hereinabove can be considerably improved by incorporatingtherein certain chemical compounds, which will be described in detailhereinafter, such chemical compounds being employed either in 15 placeof the soap or the like or in conjunction with or additions topreparations of the types hereto- These improvements manifest themselvesin various ways. The chemical compounds which are utilized are innocuousand 20 non-toxic and many are relatively tasteless. Certain of them arestable in the presence of. acids and alkaline materials and may,therefore, be employed in cosmetic preparations irrespective of the pHthereof. Many of the said compounds 25 are excellent foaming agents andare effective in comparatively small amounts to produce an excellentcleansing foam. As distinguished from soaps, the chemical compoundswhich are employed in accordance with the present invention 3 may, ifdesired, be made substantially neutral. In the case of cosmeticpreparations, their use overcomes a recognized prejudice against theemployment of soaps. In cosmetic creams, their employment results in theproduction of smooth 3;, creams having an improved texture. In general,the creams tend to be somewhat thinner and thereby spread over thesurface of the skin more easily and exert a marked softening actionthereon. In the case of dentifrices, they may be uti- 4U lized in such away as not to disturb the normal acidity of the mouth. In addition, thechemical com ounds appear to exert a bacteriostatic effect on the mouthtissues, although this matter has not yet been ascertained withcertainty. Independently of any theoretical consideration, the fact is,however, that the use of the chemical compounds contemplated herein indentifrices produces substantial improvements therein. In the case ofshampoos and hair washes, the employment of the chemical compounds inaccordance with the present invention also brings about definiteimprovements, particularly where the compounds selected are stable inthe. presence of hard water and possess marked toaminz and I o cleansingproperties.

The chemical compounds which are employed CHPOJLWH" in accordance withthe present invention are, in V 011 1 5 general, esters of certainaliphatic polyhydrlc ali J; 6

cohols with higher molecular weight aliphatic acids and preferablywater-soluble aliphatic polycarboxylic acids, especially hydroxypclycar- I Hr-0-(fCnHa boxylic acids. These compounds possess pro- I 10nounced lyophillic properties with respect to both 10 aqueous andnon-aqueous media, but particularly if in relation to aqueous media.Indeed,-this is true 13 CHr-O-C-Cgflu to such an extent that in many, itnot in most, 0H on cases, the very definitely preferred embodiments A 15represent compounds which either dispersein wa- F 11-0003 15 ter withthe greatest of ease or.- in many incm stances, readily dissolve inwaterto give clear,

transparent solutions. v r r r 7 While many of the products which areutilized V H! on on in the present invention maybest be defined in.(511-0-0-(311-323-00011 20 the form of reaction products, they andparticularly some of the more potent constituents thereof may, at leastin part, be characterized. or described by way of structural formulae;Il1us trative examples of such compounds the userot 9,5

which falls within the scope of the present in- (m on Xentron are asfollows. l v; H O C C c cm coofl c,.n== -ocm-cacrr, o-cfcncn-coon l0011' a0 0 H H H. Hr-O-CaHu 2 o 0H 11 C nit- OCHz-(JH-CHz-O-CHrCH-CIh-O-V (IJH, 15 snare-dwarf: 1 cmr-o-c-mn-cH-coon 85 HrCOONa H on u I /C!Hl mff Q 16) CnHu-C-O-CflL-N on (a) Cnlln- C-O -Cli(3H-C--OCIIr-CHCH;OH cmo-c-cnz-c-cm-coon 0H 00H (4) ll 1? I w cl1nn-c4o-cm-cm-0- -cm-cH,--:-),-o-cH,-(JH,0H CHI-000B as 3 p 311% 11 C11HaC-O- -CHr-C-OCEr-CH-CH:0H

C1Ill5C-0-CzH CzBrO-CCH;-CH-C-OH.C5H11NH1 OOH 0 on on (a c113 0Ha-c111-0-0H,- cHoH)4cHr-0-ccH,cc-oK 50 HPClOK OH c1 c1 0 55 H l II A B H(7 CnH23-COCHz H-CHg-O-C- H- H-C-O-CH;

(BHOH HIGH H OH .1 e

(a) cBa-c-ocJag-cn-cH=-oc-cHrc-cm :0H.H=N-c=mo11 M (in a n n u 66 (9 C5HCOCHr-CHr-OCCHOH-C-OH.N C;H 0H

H H I 1 CiHIOH 0 OH OH 0 o 1| 1 1 n '10 1oCnHarC-O-(CHgn-cm-o-nom-on-cru-o- -GH--OHC0H OH 0 OH 0 OH (5 t t t! t g11 C Hzr-C-(0CH1 H-cm-o- H-CH- --)|OCH: H-CHaOH I COOH 0 O CHQ-COOH OOHThe higher molecular weight aliphatic carboxylic acids which may beemployed as such, or in the form of their derivatives such as the acylhalides thereof, in the preparation of the chemical compounds utilizedherein include, among others, straight chain and branched chain,saturated and unsaturated, carboxylic, aliphatic, and fatty acids suchas caprylic acid, heptylic acid, caproic acid, capric acid, pimelicacid, sebacic acid, behenic acid, arachic acid, cerotic acid, erucicacid, melissic acid, stearic acid, oleic acid, ricinoleic acid,ricinelaidic acid, ricinostearolic acid, linoleic acid, linolenic acid,lauric acid, myristic acid, palmitic acid, mixtures of any two or moreof the above mentioned acids or other acids, mixed higher fatty acidsderived from animal or vegetable sources, for example, lard, coconutoil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil,corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanutoil, castor oil, seal oils, whale oil, shark oil and other fishoils,partiallyor completely hydrogenated animal and vegetable oils suchas those mentioned; hydroxy and alpha-hydroxy higher carboxylic,aliphatic and fatty acids such as i-hydroxystearic acid,dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid,alpha-hydroxy capric acid, alpha-hydroxy stearic acid, alpha-hydroxypalmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid,alphahydroxy coconut oil mixed fatty acids, alphahydroxy margaric acid,alpha-hydroxy arachidic acid, and the like; fatty and similar acidsderived from various waxes such as beeswax, spermacetic, montan wax,coccerin, and carnauba wax and higher molecular weight carboxylic acidsderived, by oxidation and other methods, from paraifin wax, petroleumand similar hydrocarbons; and substitution and addition derivatives ofthe aforementioned acids, in particular, halogen addition andsubstitution derivatives. It will be understood that mixtures of any twoor more of said acids may be employed if desired and it will also beappreciated that said acids may contain substituent groups such assulphate, sulphonic, nitrile, thiocyanogen, carbonyl, amide, amine orsubstituted amine, halogen, ketone, acetoxy, and other groups.

The aliphatic polyhydroxy substance which forms a part of the molecule01' the chemical compounds which are utilized for the purposes of thepresent invention may also be selected from a large group includingglycerol; glycols of both low and high molecular weight such as ethyleneglycol, propylene glycol, trimethylene glycol, butylene glycol, ceteneglycols and other vicinal glycols; 1,10 dihydroxyoctadecene; 1,10dihydroxyoctadecane, and the like; polyglycols such as diethyleneglycol; pentaerythritol; quercitol; dihydroxy acetone; triethanolamine;tripropanolamine; polyglycerols such as diglycerol, tetraglycerol andthe like including mixtures thereof; carbohydrates or sugars includingmono-, diand polysaccharides such as dextrose, sucrose, xylose,arabinose, galactose, fructose, maltose, mannose, dextrin, starch, andthe like; the natural and synthetic, simple and complex glucosides;sugar alcohols such as arabitol, mannitol, sorbitol and dulcitol; andpolyhydroxy-carboxylic acids such as tartaric acid, mucic acid,saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonicacid, trihydroxyglutaric acid, glyceric acid, carboxylic oxidationproducts of polyglycerols, others of similar character, and hydroxyethyland hydroxypropyl ether derivatives of the above, as, for example:

(For convenience, all hydroxyl groups are written facing one way.)

The polyhydroxy substance may, in certain cases, contain substituentgroups of the character set forth in connection with the discussion ofthe higher fatty acids and the like hereinabove.

' The aliphatic polycarboxylic acids and hydroxy polycarboxylic acidsmay likewise be varied and include, among others, maleic acid, fumaricacid, maleic acid, citric acid, citraconic acid, itaconic acid, aconiticacid, dichlor'omaleic acid, glutaric acid, tartaric acid, adipic acid,trihydroxyglutaric acid, succinic acid, hydroxymethyl succinic acid,mucic acid, saccharic acid, piinelic aid, suberic acid, azelaic acid,sebacic acid, the mono-' and poly-hydroxy derivatives of pimelic,suberic, azelaic and s'ebacic acids, and the like. These acids may beutilized as such or in the form of their anhydrides or esters as, forexample, the ethyl ester of citric acid. The acids may also containother substituents such as CN, NI-Iz, N02, F, Cl, Br, I, SOsH, SCN,phosphate, sulphate, etc. Tartaric and citric acids are definitelypreferred embodiments of hydroxy polycarboxylic acids which are utilizedin the production of the compounds which are employed herein.

The chemical compounds, in certain instances, may be used as such in thecosmetic preparations or they may be neutralized, in whole or in, part,with suitable anti-acid materials. In this connection, considerablelatitude and modification may be exercised. In general, inorganic aswell as organic anti-acid agents may be employed,

Examples of such agents which may be' used satisfactorily arebicarbonates of the alkali metals, potassium hydroxide, potassiumcarbonate, metallic sodium, sodium hydroxide, sodium oxide, sodiumcarbonate, ammonium hydroxide, ammonia gas, and the like; organicnitrogenous bases such as primary, secondary and tertiary aminesincluding alcohol, alkylol-, and aralkylolamines, includingmonoethanolamine, diethanolamine, triethanolamine, propanolamines,butanolamines, pentanolamines, hexanolamines, glycerolamines, sugaralkylolamines and sugar alcohol alkylolamines such as those of dextrose,sucrose, sorbitol, mannitol and the like; dimethyl monoethanolamine,diethyl monoethanolamine, dibutyl mono-ethanolamine, diethanol methylamine, diethanol ethyl amine, diethanol butanol amine, cyclohexylethanolamine, diethanol cyclohexylamine, ethanol aniline, alkylolpolyamines such as alkylol derivatives of ethylene diamine, mono-methylmono-ethanolamine, diethyl monoethanolamine, 1amino-2,3- propanediol,1,2-diamino-propanol; alkylamines such as ethylamine, propylamine,laurylamine, cetylamine, butylamine, hexylamine, cyclohexylamine,aniline, toluidines, dimethylamine, diethylamine, N-methyl-N-ethylamine, triethylamine, trimethylamine, ethylene diamine, diethylenetriamine, triethylene tetra-amine, betai'ne, mono-methyl ethylenediamine, monoethyl diethylene tetra-amine, mono-allyl amine, hydrazineand substituted hydrazine, aromatic and heterocyclic bases and cyclicnitrogenous substances such as benzylamine, cyclohexylethyl aniline,morpholine, pyridine, dimethylaniline, N-methyl-N-benzyl amine,N-ethyl-N-naphthyl amine, quinoline, quinaldine, piperidine, alkylpyridines, such as methylpyridine, pyrrolidines, nicotine, andhomologues and derivatives or substitution products thereof, and, ingeneral, primary, secondary and tertiary amines substituted or not withother radicals, such as hydroxy, alkyl, aryl, cyclo-alkyl groups and thelike; quaternary ammonium bases or hydroxides such as tetra-methylammonium hydroxide, tetra-ethyl ammonium hydroxide, quaternary ammoniumbases with dissimilar alkyl radicals such as methyl-triethyl ammoniumhydroxide, propyl trimethyl ammonium hydroxide; mixtures of any two ormore of said bases, as, for example, in the case of commercialtriethanolamine which contains minor proportions of monoanddiethanolamine; proteins and partial digestion or hydrolysis productsthereof. It will be understood that these substituted ammonium compoundsor organic nitrogenous bases -may be utilized in pure, impure, orcommercial form.

It will be understood that by the term cation, as used throughout thespecification and claims,

is meant hydrogen and such other elements as are mentioned herein, and,in general, atoms or radicals which are regarded as bearing a positivecharge or capable of replacing acidic hydrogen. The chemical compoundsmay be neutralized to methyl orange, litmus or phenolphthalein or to anydesired hydrogen ion concentration. As a general rule, if the salts ofthe chemical compounds are employed, it is preferred to use the sodium,potassium, ammonium, alkylolamine, or other soluble salts.

A particularly important group of the chemical compounds which areutilized herein are those wherein the-pattern or linkage between thealiphatic polyhydroxy substance and the aliphatic polycarboxylic acid orhydroxy polycarboxylic acid repeats itself in the molecular structure.This pattern is not, however, repeated to such an extent as to impair ordestroy the water-solubility or ready water-dispersibilit'y of thechemical compounds. This pattern repetition is illustrated by Examples 4and 11 in the compounds listed hereinabove.

The following examples are illustrative of the preparation of thechemical compounds which may be "employed in accordance with the presentinvention. It will be appreciated that the proportions of reactingingredients. times of reaction, temperatures of reaction, and the likemay be varied and that supplementary processes of purification and thelike may be resorted to wherever found desirable or convenient. Theseand other variations and modifications will be evident to those skilledin the art in the light of the guiding principles which are disclosedherein.

Example A (1) 34.8 parts bylweight of glycerin and 28.4 parts by weightof tartaric acid were heated, provision being made for water of reactionto escape, with stirring, for about 5 hours at a tem-- perature between120 degrees C. and 140 degrees C. at the end of which time a smallamount of free tartaric acid remained, the balance having reacted withthe glycerin to form esters therewith.

(2) 7.9 parts by weight of the reaction product of part (1) weredissolved in parts by weight of hot, dry pyridine, the solution wascooled, and 5 parts by weight of lauroyl chloride were added. The masswas periodically agitated and allowed to stand over night and was thenextracted with petroleum ether. The petroleum ether adhering to theresidue was then evaporated in vacuo at 100 degree C. The final reactionproduct contained a substantial proportion of compounds having one orboth or the probable formulae In order that those skilled in the art mayeven more iully understand the nature of the 1nven= O-JL-Onlin (1) 276parts by weight of glycerin and 192 parts by weight of citric acid wereheated, water of reaction being permitted to escape, with stir: ring,for about 6 hours at a temperature ranging from 140 degrees C. to 155degrees C at the end of which time some free citric acid remained.

(2) 78.85 parts by weight of the reaction product of part (1) hereofwere dissolved in 200 parts by weight of dry pyridine, the solution wascooled, and 5'? parts by weight of stearoyl chloride were graduallyadded while cooling and stirring. The mass was allowed to stand forseveral hours and was then extracted with petroleum ether. The remainingbrown syrup was then freed oi adhering petroleum ether by heating at 108degrees C. in vacuo. It had good foaming properties and comprised abrown, syrupy material, a major portion of which had the probableformula (1) 192.25 parts by weight of propylene glycol and 189.8 partsby weight of tartaric acid were heated, with stirring, for 8 hours at atemperature ranging from 135 degrees C. to 170 degrees C., the resultingester being a viscous, glassy syrup containing some unreacted tartaricacid.

(2) 23.2 parts by weight of the ester reaction product of part (1)hereof were dissolved in 75 parts by weight of dry pyridine, thesolution was cooled, and 27.5 parts by weight of palmitic acid chloridewere gradually added while cooling and stirring. The mass was permittedto stand for several hours and was then extracted with petroleum ether.The residue, freed from adhering petroleum ether, showed good foamingproperties and had the probable formula on OK on on; ICHz-CH-CHz-O(%-CH-OH-fi-O-HaC-HCO%C1|Hu It is evident that various ofthe chemical compounds which are employed herein may be produced indifierent ways. Thus, for example, the mono-succinic acid ester ofmonolaurin may be prepared by reacting monolaurin with succinic acidanhydride. Alternatively, it may be prepared by reacting themono-succinic acid ester of glycerin with lauroyl chloride. Theparticular method selected will depend upon various considerations suchas cost and availability of reacting ingredients, simplicity ofprocedure, yields of the desired compounds, and the like.

tion, the following examples are set forth hereinbelow. It is, however,to be understood that said examples are merely illustrative and are in yno wise to be construed as limitative oi the invention. All parts listedare by weight except where otherwise indicated.

(1) Tooth paste Parts Precipitated chalk 110 Glycerine '75 Product ofExample A 3 Gum tragacanth 2.7 Water 100 Flavor to suit.

(II) Tooth paste Parts Precipitated chalk-light 100 Tricalcium phosphate75 Soap powder 10 Product of Example A 5 Gum tragacanth 0.2

Mixture of glycerin, honey and water in amount sumcient to give desiredconsistency. Flavor to suit.

(III) Vanishing cream (VI) Hair shampoo A solution, in water, of themonoethanolamine salt of the mono-tartaric acid ester of monolaurin.

The compositions described hereinabove are made in the usual way thatsuch preparations are made. Thus, for example, the chemical compoundsdisclosed herein may be preliminarily incorporated in the oleaginous orwaxy material of the cosmetic preparations or dispersed in the aqueousmaterial prior to incorporation therewith of any remaining ingredients.However, the chemical compounds disclosed should preferably not becontacted with strong alkalis, such as concentrated caustic sodasolution.

It will be understood that the chemical compounds need not be utilizedin the pure state. Indeed, in most instances it will be found to be moreconvenient and commercially desirable to employ them in the form oftheir reaction mixtures with or without the addition of diluents. Itwill also be understood that mixtures of any one or more of the reactingconstituents may be employed in producing the products hereof and thisis particularly the case where commercial supplies of the chemicals areutilized. It will also be appreciated that any of the polyhydroxysubstances listed hereinabove may be reacted with any of thepolycarboxylic acids and higher molecular weight acids to produceproducts which are useful for the purposes or the present invention.

it will also be understood that the proportions of the previouslydescribed chemical compounds employed in the cosmetics may be widelyvaried, depending upon various factors such as the nature of theparticular cosmetic, the effectiveness of the particular chemicalcompound selected, the specific results sought, and the like. In general, in the creams and dentifrices, the proportions will vary fromunder 1% to as high as 10% or more, a preferred range usually being from1% to 3.5%. In hair washes and shampoos, between about and 20% andsomewhat higher is eifective, about 12% to 18% representing asatisfactoiy average.

It will be seen from a consideration of the numerous examples listedhereinabove that the chemical compounds which are employed herein fallinto two categories, namely (1) wherein they are derived from monomericpolyhydroxy substances or polyhydric alcohols, exemplified by glycerol,ethylene glycol, and the like, and (2) those which are derived frompolymeric alcohols, exemplified by diglycerol, triglycerol,tetraglycerol, and the like, it being understood that the term polymericis used herein to denote alcohols containing more than two esterifiablehydroxy groups. Of particular utility herein are the monomericderivatives.

Again, the compounds utilized herein may be classified with respect tothe absence therein of free or unesterified carboxyl groups. Thoserepresented by Numbers 4, 7, 11, 22, 23, and 24 fall into this categorywhereas the other compounds are characterized by the presence of free orunesterified carboxyl groups. In certain cases, those which fall intothe group represented by Numbers 4, 7, 11, 22, 23 and 24 are especiallyuseful.

The term fatty constituent, as used in the claims, will be understood toinclude not only conventional fats and oils, whether of animal,vegetable or mineral origin, but also higher molecular weight carboxylicand fatty acids as well as waxes, and, in general, any material having agreasy character and which is immiscible with water.

The term higher, as used herein and in the claims to describe carboxylicand fatty acids and the like, will be understood to mean at least sixcarbon atoms unless otherwise specifically stated.

While the invention has been described in de tail, it is to beunderstood that the scope thereof is not to be limited other than as setforth in the claims.

wherever the chemical compounds are referred to in the claims, it willbe understood that it is intended to cover them irrespective of whetherany free carboxyl groups therein are neutralized or not. In other words,the language employed will include compounds wherein the hydrogen ofcarboxylic groups is present as such or is replaced by another cation,unless the connotation otherwise expressly indicates otherwise.

The term poly wherever used herein, unless otherwise specificallystated, will be understood to be employed in its usual sense, namely, todenote two or more.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A cosmetic preparation containing a proportion of a chemical compoundin the form of a lyophillic higher molecular weight aliphatic acid esterof an ester of an aliphatic polyhydroxyl substance with an aliphaticpolycarboxylic acid.

2. A cosmetic preparation containing a proportion of a chemical compoundin the form of a lyophillic higher molecular weight fatty acid ester or"an ester of a monomeric aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

3. A cosmetic preparation containing a proportion of a chemical compoundin the form of a lyophillic higher molecular weight fatty acid ester ofan ester of glycerin with an aliphatic polycarboxylic acid.

4. A cosmetic preparation containing aproportion of a chemical compoundin the form of a lyophillic higher molecular weight fatty acid ester ofan ester of glycerin with a water-soluble aliphatic hydroxypolycarboxylic acid containing not more than six carbon atoms.

5. A cosmetic preparation containing a proportion of a chemical compoundin the form of a lyophillic higher molecular weight aliphatic carboxylicacid ester of an ester of glycerin with tartaric acid.

6. A cosmetic preparation in accordance with claim 5 wherein the highermolecular aliphatic carboxylic acid radical comprises a lauric acidradical.

7. A cosmetic cream containing a fatty constituent and a proportion of achemical compound in the form of a lyophillic higher molecular weightaliphatic acid ester of an ester of a polymeric aliphatic polyhydricalcohol with an aliphatic polycarboxylic acid.

8. A cosmetic cream containing a fatty con stituent and a proportion ofa. chemical compound in the form of a lyophillic higher molecular weightfatty acid ester of an ester of an aliphatic polyhydric alcohol with analiphatic polycarboxylic acid.

9. A cosmetic cream comprising an emulsion of oleaginous and aqueousmaterials and containing a proportion of a chemical compound in the formof a lyophillic higher molecular weight aliphatic acid ester of an esterof a monomeric aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

10. A cosmetic preparation comprising an emulsion of oleaginous andaqueous materials, the oleaginous material comprising predominantly anormally solid higher molecular weight fatty acid, and containing aproportion of a chemical compound in the form of a lyophillic highermolecular weight fatty acid ester of an ester of a polymeric aliphaticpolyhydric alcohol with an aliphatic polycarboxylic acid.

11. A dentifrice containing in addition to the usual dentifriceingredients a proportion of a chemical compound in the form of a.lyophillic highermolecular weight aliphatic acid ester of an ester of analiphatic polyhydric alcohol with an aliphatic polycarboxylic acid.

12. A dentifrice comprising a salt of the class consisting of tricalciumphosphate, dicalcium phosphate, and calcium carbonate in admixture witha chemical compound in the form of a lyophillic higher molecular weightfatty acid ester of an ester of an aliphatic polyhydric alcohol with analiphatic polycarboxylic acid.

13. A cosmetic preparation in the form of a hair shampoo comprising anaqueous solution of a chemical compound in the form of a lyophillichigher molecular weight aliphatic acid ester of an ester of an aliphaticpolyhydric alcohol with an aliphatic polycarboxylic acid.

14. A cosmetic preparation in the form of a hair shampoo comprising anaqueous solution of at least 5% by weight of a chemical compound in theform of a lyophillic higher molecular weight fatty acid ester of anester of a monomeric aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

15. A cosmetic preparation in the form of a hair shampoo comprising anaqueous solution of at least 5% of a chemical compound in the form of anitrogenous base salt of a lyophillic higher molecular weight aliphaticacid ester of an aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

16. A cosmetic preparation in the form of a hair shampoo comprising anaqueous solution of at least 5% of a chemical compound in the form of analkylolamine salt of a lyophillic higher molecular weight fatty acidester of an aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

1'7. A cosmetic preparation containing a proportion of a chemicalcompound in the form of a lyophillic higher molecular weight aliphaticcarboxylic acid ester of an ester of glycerin with citric acid.

18. A cosmetic preparation in accordance with claim 1'7 wherein thehigher molecular weight aliphatic carboxylic acid radical comprises alauric acid radical.

19. A cosmetic preparation in the form of a hair shampoo comprising anaqueous solution of at least 5% by weight of a chemical compound in theform of a lyophillic higher molecular weight fatty acid ester of anester of a polymeric aliphatic polyhydric alcohol with an aliphaticpolycarboxylic acid.

BENJAMIN R. HARRIS.

